Method of chlorination



Nov. 26, 1935;

B. GALLSWORTHY 2,022,619 METHOD OF GHLORINATION Filed Jan. 19, 1955BE/lUflM/V GWALSWOPTHY? 11v VENTOR 5 A TTOR/VEY catalysts and promoters.

Patented Nov. 26, 1935 METHOD OF CHLORINATIQN Gallsworthm'Glenham, N.Y., casino: to The-Texas Company, New York, N. Y a. corporation ofDelaware Application January 19,1933, Serial No. 652,491

Claims. (cl. 260-102) This invention relates to the chlorination ofpetroleum hydrocarbons and more particularly to the chlorination ofpetroleum hydrocarbon oils.

More specifically, my invention relates to the chlorination of petroleumhydrocarbon oils by contacting them with an aqueous solution ofhypochlorous and hydrochloric acids whereby the petroleum hydrocarbonoils are chlorinated to the desired chlorine content.

A large number of chlorination methods have been proposed in the past.Some of these have featured the chlorination of petroleum hydrocarbonsby reacting them with gaseous chlorine in the presence of ultra-violetlight or chemical Other methods have disclosed the interaction ofhydrocarbon oils and chlorine in the presence of contact catalysts andunder varying conditions of temperature and pressure. These methods,when applied to the chlorination of petroleum hydrocarbon oils, have.

been found to result in the discoloration of the oils, the formation ofsludges, as well as in the production of large quantities of undesirablechlorinated lay-products. The reactions are either extremely slow orelse when accelerated by increasing the temperatures, pressures orchlorine concentration tend to proceed violently and may, in many cases,result in the utter decomposition of the petroleum hydrocarbon oil.

In accordance with my process, petroleum hy-v and then agitating apetroleum hydrocarbon with this chlorine water whereby a smooth andcomplete chlorination of the petroleum hydrocarbon is effected. i

The use of ultra-violet light, reaction catalysts, contact agents orreaction promotors is unnecessary. The reaction proceeds quite rapidlyand there is no apparent production of exothermic energy. Petroleumhydrocarbon oils chlorinated in accordance with my invention are notdiscolored and do not contain any sludge, nor does the chlorinated oilsuffer from the formation of undesirable, unsaturated hydrocarbons dueto the cracking of the unstable petroleum hydrocarbons. My invention isreadily applicable to all types of PATENT OFFICE petroleum hydrocarbonsand elaborate apparatus is unnecessary for carrying out the process.

The herein disclosed invention may be applied in a variety of ways. Forexample, a petroleum hydrocarbon oil may simply be agitated with 5chlorine water for a sumcient period of time to permit the reaction totake place, or else the, oil may be mixed with chlorine water in a towerfilled with contact materials such as Raschig rings, coke or refractorymaterials. The process also lends itself quite successfully toapplication in a countercurrent process wherein the petroleumhydrocarbon oil is flowed countercurrently to a stream of chlorinewater. Here the oil and chlorine water are successively agitatedtogether and separated, the 'unchlorinated hydrocarbon oil beingcontacted with chlorine water containing the lowest percentage ofhypochlorous acid and the most highly chlorinated hydrocarbon oil cominginto contact with the highest concentration of hypochlorous acid.

The accompanying drawing discloses an apparatus suitable for carryingout my invention and the following description taken in connectiontherewith will serve for a better understanding of 'my invention.

The numeral II indicates a tank for untreated oil. This tank is providedwith a drawoff line H fitted with a valve I! which connects the tankwith the intake side of the pump l3. This pump discharges through theline H controlled by the valve I5 into the mixing chamber l6. Thismixing device may be of any suitable construction. It is fitted aroundits circumference with heating coils through which a suitable heatingmedium may be circulated. These coils are indicated by the numeral 11.It is also equipped with a mechanical agitating device 88 which is usedfor bringing the untreated oil into intimate contact with chlorinewater. The bottom of the mixing 4 chamber I6 is provided with a draw-offline it controlled by the valve 26 which line discharges into thesettling chamber 2! wherein the partly chlorinated oil separates fromthe spent chlorine water. The latter is drawn off from the bottom of thesettling chamber through the drawofi line 22 controlled by the valve 23.

The top of the settling chamber 2! is equipped with a drawoif line 24controlled by the valve 25 through which the partly chlorinated oildrawn 59 off from the top of the settling chamber is delivered into themixing chamber 26. The mixing chamber 26 may advantageously be of thesame construction as the previously described; mixing chamber it.

Q mixing chamber 26 is connected by means of the line 21 controlled bythe valve 28 with a source 29 of chlorine water. This source consists ofa chamber wherein water and chlorine gas are reacted to form an aqueoussolution of hydro-- chloric and hypochlorous acids which is spoken ofherein as chlorine 'water. The chamber is preferably fitted-with afilling 30- of refractory material which assists in the properinteraction of the water and gaseous chlorine. This material ispreferably supported on the perforated tray 31 at a small distance abovethe bottom of the chamber. Gaseous chlorine is delivered into the bottomof the tower throughthe line-32 controlled by the valve 33 while wateris injected through the line 34 controlled by the valve 35 at a pointabove the tray' 3l.

The mixing chamber 26 is fitted at its bottom with a drawofi line 3'!controlled by the valve 38 which connects it with the settling chamber39 wherein the chlorinated oil-is separated from the partly spentchlorine water. The chlorinated oil is drawn off ,from-the top of thesettling chamber through the'llne 40 controlled by the valve 4| anddelivered to the storage tank 42. The bottom of the settling chamber 39is fitted with a drawoff line 44 controlled by the valve 45 which leadsto the mixing chamber l8.

In a typical operation of my invention in connection with the apparatusshown in Figure 1, a petroleum hydrocarbon oil which is to bechlorinated, is drawn from the storage tank It) and passed to the chargepump l3 by which it is delivered under suitable pressure through theline H into the mixing chamber l8. Herein the untreated oil isthoroughly agitated at an elevated temperature with partly spentchlorine water from a succeeding step in the process. The hypochlorousacid readily reacts with the hydrocarbon oil to form substituted chlorcompounds. The mixture of partly chlorinated oil and spent chlorinewater is drawn off from the bottom or the mixer l6 and delivered intothe settling chamber 2| wherein a substantial separation of the oil andwater is brought about. The spent chlorine water is drawn oil throughthe bottom drawofl. line 22 controlled by the valve 23 and delivered toa suitable storage tank or, ii desirable, to a hydrochloric acidconcentration system.'- The partly chlorinated 011 which forms thesupernatant layer in the settling chamber 2| is drawn vofl! through theline 24 and delivered into the mixing chamber 26 wherein it is agitatedwith a proportioned amount of fresh chlorine water.

The chlorine water used-in the operation of this process is prepared inthe chamber. 29. Herein correctly proportioned quantities of waterandgaseous chlorine are intermixed and interacted to form an aqueoussolution of hydrochloric and hypochlorous acids. This solution isdelivered into the mixing chamber 28 through the line 21.

The partly chlorinated oil and fresh chlorine water react quite readilyand the mixture'which is drawn or! from the mixing chamber 28 throughthe drawoif line 21 consists essentially of chlorinated oil and partlyspent chlorine water. These two materials are substantially separated inthe settling chamber 2!, the partly spent chlorine water being deliveredto the mixing chamber l8 through the line 44 while the chlorinated oilis drawn off from the top of the chamberthrough the line anddeliveredlto-the storage tank 42. i l

The chlorination process be applied any petroleum hydrocarbon oil irre ptive of its viscosity, the only requirement being that it be fluidenough at elevated temperatures to permit of its being readily reactedwith the chlorine water. As an example of how the process may be appliedto various petroleum hydrocarbons. I an .oil having the following testsmay be submitted to treatment:

Gravity, A. P. I l;;r; r. Visc. Univ. at 100 F 183 Pour, "F 25- X Byinteracting this oil with a chlorine water at a' temperature T01approximately 150 F. and under-a; pressure of 25 lbs. per sq. in., achlorinated oil having the following tests may be produced: ll 1Gravity, A. P. I 20.2 Visc. Univ. at 100 F 305 Visc. Univ. at 210 F 52Pour, r 15 m Chlorine, per cent... 5.81

.Speciiic'gravity'at 60 1'' 1.014 Flash -i 535 Fire- 5'10 Visc. Univ. at100 F 828 Solid point F Chlorine content per cent; 23.20

The temperatures used in the operation of process lie preferably in therange of from to 200 F. although higher or lower temperatures may befound especially applicable in chlorinat- 0 ing certain hydrocarbons.Similarly. the pressures used while interacting petroleum hydrocarbonoils and chlorine water are preferably below 500 lbs. per sq. in.

In actual practice it is found that certain hydrocarbons are lessreactive than others and that their hydrogen atoms are .not as readilyreplaced by chlorine. Such oils require longer time of contact with thechlorine water as well as'hisher temperatures and pressures. The longertime o! contact in an apparatus such as that shown in Figure 1 isreadily obtainable by reducing the rate of flow of the oil whilesubstantially increasing the quantity of chlorine water used. '.In this1 manner smaller volumes of petroleum h'ydroc'arbon oil are contactedwith proportionately larger quantities of chlorine water andthe flow"rites being low, these two materials will be contacted forproportionately longer periods of time.

Obviously many modifications and variations of n the invention, ashereinbeiore set forth. may be 1 made without departing from the spiritand scope thereof, and therefore only such limitations should be imposedas are indicated in the sppendedclaims.' u

I claim: 1. The method of chlorinating hydrocarbons which comprisesagitating petroleum hydrocorbons selected from the group consisting oflubricating oils and paraihn war with an'aqueous so- 7 lution ofhydrochloric and hypochlorous with at a temperature in therange of to200' l". and under a pressure of between 20 and 500 pounds .per squareinch.

2. The method oilchlorinatinl II r which comprises agitating petroleumhydrocarbons selected from the group consisting of lubricating oils andparatlln was with chlorine water at a temperature of about 150 1''. andunder a pressure of about .25 pounds per square inch.

3. The method of chlorinating hydrocarbons which comprises agitatingpetroleum hydrocarbons selected from the group consisting oi lubricatingoils and paraflln wax with chlorine water at a temperature of between150 and 200' I. and under a pressure oi between 25 and 500 pounds persquare inch to form a mixture, and then subjecting the mixture tosettling to eilect the separation of the chlorinated hydrocarbons fromthe spent chlorine water.

4. The method of chlorinating hydrocarbons which comprises alternatelymixing petroleum hydrocarbons selected from the group consisting oflubricating oils and paraflln wax and separating them from acountercurrently flowing stream of chlorine water while maintained at atemperature in the range oi'150' to 200' it. and under superatmosphericpressure, the unchlorinated by;

drocarbons coming into contact with partly spent chlorine water and thepartly chlorinated hydrocarbons coming in contact with iresh chlorine g5. The method oi chlorinating hydrocarbons which comprises flowingpetroleum hydrocarbons selected from the group consisting of lubricatingoils and paraflln wax while maintained at a temperature in the range of150 to 200 1. and under i apressure of between 25 and 500 pounds persquare inch countercurrently to a stream 0! chlorine water, therelatively unreacted hydrocarbons coming into contact with partly spentchlol5

